Azo dyestuffs



Patenteci Aug. 8, 1950 AZO DYESTUFFS Ernst Keller and Fritz Probst, Basel, Switzerland,

assignors to J. R. Geigy A. G., Basel, Switzerland No Drawing. Application October as, 1947, Serial No. 781,748. In Switzerland October 31, 1946 '7 Claims. (01. 260-175) This invention produces valuable new azo dyestuffs.

Such azo dyestuffs can be obtained by submitting 2 molecular proportions of an aminoazo dyestuff of the general formula:

R1 means the radical of an O-a'cyl-1-amino-8- hydroxy-naphthalene-3 6-disulphonic acid and R2 means the radical of a primary aromatic amine coupling in the p-position to the amino group I together with 1 molecular proportion of a monoor polynuclear aromatic compound containing two primary amino groups, not in the o-position relative to one another, e. g. an aromatic monoor polynuclear diamine capable of being di'-. acylated, and when necessary, further. containing in particular. water-solubilizing groups, to the action of phosgene untilthe, amino groups are completely transformed and subsequently splitting ofi the acyl radicals from the O-acyl groups. As diazo components from the group of O-acyl derivatives of 1-amino-8-hydroxynaphthalene- 3:6-, or -4:6-disulphonic acids areusedtheO-benzene-sulphoand especially the O-p-toluene-sulpho-l-amino 8 hydroxynaphthalene-3:6- or -4:6-disu1phonic acids. The mostsatisfactorycoupling components are: l-amino-B-methyl-G- methoxyand -6-etho y benzene. Out of the large number of monoor polynuclear diamines the following are those mainly used: p-phenylenediamine, m-phenylenediamine; p-phenylene-diamine-sulphonic acid, p-phenylene-diamine-carboxylic acid, benzidine; o-toluidine, o-dianisidine, benzidine-Z :2 -disulpho-nic acid, benzidine-3 3'-disulphonic acid, benzidine-B-sulphonic acid, 4:4'-diamino-diphenylurea3 :3 -disulphonic acid, 4 4'- diamino+diphenylurea-2:2'-disulphonic acid, 1-

methyl-Z 6-diaminobenzene-4-sulphonic acid, 4'-

aminobenzoyl-p-phenylene'- diamine sulphonic acid, 3'-aminocinnamoyl-p-phenylenediamine sulphonic acid, 4:4-diaminosti1bene, 4:4'-diarhinostilbe'ne-Z :2 -disulphonic acid, 4-amino-4- (p aminobenzoyl) aminostilbene 2 :2'-disul- Phonic acid." 4 amino-4'-(m-amino-benzoyl acid, In phenylenediamine-sulphonic aminostilbene-Z :2 -,disulphonic acid, 4 :4 -di- (paminobenzoyl) diamino stilbene 2 :2 disulphonic acid, 4:4-diaminodiphenylmethane, 1:5- diaminonaphthalene-3 7 -disulphonic acid, 2 S diaminonaphthalene-8-sulphonic acid, 6:6 -diamino 2:2'-dinaphthylurea 8:8-disulphonic acid, 2 :7 4 diaminonaphthalene, 1:5-di- (p-aminobenzoylamino) -naphthalene 3:7 disulphonic acid, 1:5 di (m-aminobenzoylamino)-naphthalene- 3:7-disulphonic acid.

The new dyestuffs are dark powders giving a red solution in water and dyeing cellulose fibres in valuable clear red tints distinguished by good light-fastness and also good fastness properties when wet. a I

Dyestuffs have already been described which are preparable 'by stepwise condensation of 2 molecular proportions of an amino-azo dyestufi produced by coupling the diazotised O-p-toluene sulphonic acid ester of 1-amino-8-hydroxynaphthalene-3:6-disulphonic acid with 1-amino-3- methyl-6-methoxy-behzene, with 2 molecular proportions of cyanuric chloride and 1 molecular proportion of either 4:4-diaminostilbene-2:2'-disulphonic acid or 4:4-diaminostilbene. It is further possible to replace the third halogen atom by an amine radical. It is true that the reaction leading to the manufacture of the above mentioned dyestuffs has been known for a long time, i. e., the stepwise replacement of the three halogen atoms of a cyanuric halide by amines by a suitable choice of reaction temperature. However, it is new and very surprising to find that 2 molecular proportions of one of the azo dyestufis claimed in the invention form symmetrical di-urea derivatives with phosgene and one'molecular proportion of a primary diamine, Whose amino groups are not in thee-position relative to one another.

These new dyestuffs clearly have the following general formula:

where Y means the radical of a diamine as hereinbefore defined.

As compared with the dyestuffs mentioned above, the red shades produced by the new dye 3 stuffs are less yellowish. In addition they exhibit better drawing properties and, in. general, better fastness to washing and to water. Furthermore, a considerable number of them have better fastness properties towards acids and alkalis. Another valuable property possessed by the new dyestuffs is that dyeings yielded b them on cellulose fibres alter in shade very little, if at all, when after-treated with compounds used to improve water-fastness properties. It is Well known that anti-creasing treatment of woven textiles is of ever-increasing importance in the improvement of such materials. There are only comparatively fjew'direct dyestuffs, however which are not noticeably changed in shade or light fastness by this treatment. The dyestuffs pre parable according to the invention are distinguished in that very little change in shade, in particular, and in fastness to light ingeneralis.

brought about by the above-mentionedtreatment. This is all the more valuable since this property has so far hardly been known among the red, direct-dyeing dyestufis.

The following examples serve-further-taexplain 62.1 parts of the monoazddyestulf; prepared in the usual way. by diazotising theip-toluenesulphonic, acid ester of 1-amino-8-hydroxynaphthalene-3zG-disulphonic acidand coupling.

the .diazo, compound with 1-arninm3-methyl-6- methoxybenzene are dissolved;together-with. 18 .5. parts of 4 :4 -diaminostilbene.-2 :2 -disulphonio acid in about 800 parts of water by the addition of sodium, carbonate.

Phosgene is passed, into, the solution, which should be neutral or slightly alkaline (upto the alkalinity oi bicarb,onate)-in this case with advantage in the presence; of sodium, acetateuntilino more primary aminecan be detected in a test-sample. The condensation product is precipitated outwith common-salt and'filtered ofi..

In order tov split off the p-toluene-sulphonic acid group, the dyestufi is heated in dilute caustic alkalisolution at Bil-90 until complete saponification of the p-toluene-sulphonic acid ester. saponified dyestuff, which partly crystallises out oncoolingis completely precipitated by the addi- Lionv of common salt, filtered ofi and dried.

It dyes cellulose fibres to give clear redshades which have. ver good fastness properties towards light, washing and water;

Emample 2 62.1 parts of the monoazo dyestuff from the diazotised p-toluene-sulphonic acid ester of 1'-amino-8-hydroxy-naphthalene3 6 -disulphonic acid and -1 amino-3-methy1-6-methoxybenzene are dissolved together with 132 parts of benzidine-S-sulphonic acid in about 750 parts of water. by theaddition of sodium carbonate.

Treatment-with phosgene is then continued as described in the previous example until no more diazotisable amine. can be detected, inv a testesample.

After splitting ofi'the p-to1uene-sulphonic acid group by warming. the; dyestufi obtained in the condensation with phosgene in dilute caustic alkali solution at 80.-90?, a dyestuff is obtained which, dyes cellulose, fibres in clear red tones,

The

, red tones.

towards light, washing and water.

possessing good fastness properties towards light, water and washing.

Example 3 Example 4 621 parts-of the-monoazo dyestuff from the diazotised p-toluene-sulphonic acid ester of 1-amino-8 hydroxynaphthalene-3 6-disulphonic acid and 1-a-mino-3-methyl-6-methoxybenzene are; dissolved in about 1200 parts of water by adding, sodium carbonate and made slightly acid to litmus with acetic acid. To this solution are added 5.4 parts of m-phenylenediamine dissolved in 108' partsof'water made acid to litmus:

Phosgene is passed into the solution, preferably containing sodiunr acetate; until a test-sample canno longer be diazotised. The-reaction of the solution is maintained just acid to litmus durin the addition of; phosgene by gradually adding dilute sodium carbonate solution. The condensation product is precipitated with commonsalt and filtered off..:

After the p-toluene sulphonic acidester. has been saponified, in the-waydescribed. in previous examples a. dyestufi? isv obtained which dyes cellulose fibres in clear red shades, somewhatl more yellowish than. those given by the dyestufis of Examples- 2 and 3.

Example 5 62:1 parts of the monoazo: dyestuff from the diazotised p-toluene-sulphon-ic acid ester of' 1 -amino-8-hydroxynaphthalene-3': G-disulphonic acidand. 1-amino-3-methyl-G-methoxy benzene are dissolved-togetherwith. 3024: parts of 4:4 -di.- (p--.=aminobenzoyl) diaminostilbene .2:2' disulphonic. acid intabout .2800 parts of water: by adding sodium. carbonate.

Phosgene ispassed'into-thesolution, preferably. weaklyralkaline', .asdescribediinprevious'examples and. after separatingthe condensation product the p-toluene;-suliphonic; acid group is. split off. The. dyestuffi obtained-.dyesxcellulose fibres in redshades-whichare fast to light.

Example 6 62.1; partsof: the monoazoidyestufi prepared by diazotising the'p-toluenesulphonic acid ester of 1.-amino-8-hydroxy naphthalene-.4 6-disulphonic acid...and; coupling. the diazo. compound with 1-amino-3-methyl+oemethoxybenzene are dissolved together with 18.5 parts of 4:l'-diaminostilbene-2:2-disulphonic acid in about 800 parts of water. by adding sodium carbonate. This;.solution is treated with phosgene under the conditionsdescribed in Example 1 until no. more primary amine can be detected in a testsample. Thecondensation product is then precipitated WiChtCOmlnOl'l salt and filtered off. Next, the p-toluene-sulphonic aoidgroup is split on". by heating in dilute caustic-alkali solution at 89,-9.01 The sappnified. dyestuff. partly; crystal L... lizes out on ci1-in precipitation-is completed .by. addin common salt. and.--thezproduct filtered off.

The new dyestuff gives red dyeings on cellulose fibres which are more bluish than those given the conditions described in Example. l until no. I

more primary amine can be detected in a testsample. The, condensation product formed is precipitated by adding common saltand filtered on. Thefben zenesulphonic acid groups are split off by warming in dilute caustic alkaline solution at 80-90". The saponified 'dyestufl partly crystallises out on coolinggrit is completely precipitated with common salt and filtered off.

The new dystufl dyes cellulose fibres in yellowish-red: shades which have good light-fastness properties. v

* Example 8 Exactly the same procedure as in Example '7 can be employedwithfiilfl parts of the mo'noazo dystuff named therein or 62.1 parts of the corresponding monoazo dystufi prepared fromthe ptoluene-sulphonic acid ester of 1:8-amin onaph thol-3z6-disu1foni6 acid and 25.1 part'sfof 6:6- diamino-2:2';- dii'iaphthylurea 8:8 disulphonic acid '(A). The action of phosgene on these components dissolved in about 870 parts of water-joilowed by splittingofi the p-toluenef sulphonicacid group yields a new dystuff which also dyes cellulose fibres in somewhat yellowish red shades possessing good fastness to'light.

Compound A is prepared by the action of phosgene on G-nitro-Z-aminonaphthalene-ii sulphonic acid, followed by reduction of the nitro, compound obtained by Bchamps method. i

10 Example 9 62.1 parts of the monoazo dystuff from the di- ;azotised p-toluene-sulphonic acid ester;of;r1;:8 amino hydroxy naphthalene -i 3z 6 -disu;lphonic acid and 1-amino-3-methyl-6-inethoxybenzene are dissolved with sodium carbonate in about 1200 parts of water and made weakly acid to litmus with acetic acid. To this solution are added 7.9 parts of 1:5-naphthylenediamine dissolved in. 158 parts of water made acid to litmus. Q

The reaction mixture (whichshould be acid to litmus) is then submitted to the action of phosgene; advantageously in the presence 'of -sodium' acetate, until no more primary amine can be detected in a test sample. The condensation product-formed is precipitated out with common salt and filtered ofi. After splitting all the p-toluenesulphonic acid groups by heating in dilute caustic alkali solution atf80-90" anew dyestuff is obtained 30 which dyes cellulose fibres in red shades which have good light-iastness properties. In the following "table are collected together a few further dyestufis preparable according to the'invention by condensing an aminoazo dyea stuff and a diamine with phosgene, followed by the'splitting oil of the" acyl group. The method of manufacture is exactly analogous to that given in the preceding examples.

. Dyeing on No. 1 Aminoazo Dyestufl Dlamlne llulose Fibres 1 p-Toluenersulphonic acid ester of 1-ainino-8;hydroxyna h- 4-Ai nino-4-(p-an imobenzoyl)-aminostilbeiie-2:2- red.

thalene-3z6-disulphonic acid l-amino-3-methy -6- disulphonic acid. methoxybenzene. d 4-Amino-4'- (m-amiiiobenzoyl) -ammostilbene- Do.

2:2-disulplionic acid. 1

p-Phenyleiiediamine sulphonic acid D m-Phenlyenediamine sulphonic aci D Benzidine-2:2-disi1lphonic acid 13 Benzidine-3:3-djsu1phonic acid D 4:4'-Diamino-diphenyl-urea-3:3-disu1phon D 4- A mi%obenzoyl-p-phenylene-diamii1e sulphon- Do.

10 aci 1-Metl yl-2:6-diamino-benzene-l-sulphonic acid Do.

4:4-Diamino-diphenylamine-2-sulphonic acid Do.

Benzidine-3:3'- dicarboxy1ic acid D p-Phenylene diamine D 4-Aminobenzoyl-p-phenylene diamine Do.

Bprwi'dine D o-Din'nisidine 4:4-Diaminordiphenyl-methane 4:4'-Diamino-diphenyl-sulphide do. p-Toluene-siilphonic acid ester of l-amino-S-hydroxynaphthalene-zG-disulphonic acid l-a nino-ii-methyl-fi-me- 4:4'-Dip-aminobenzoyD-diamin disulp onic acid.

thoxybenzene. 21 do. 4-Ainino-4-(p-aminobenzoyl)-aminostilbene- Do.

2:2-disii1phonic acid. 22 do- 4-Amino-4-(m ammobenzoyl)-aminostilbene- Do. 2:2-disulphonic acid. p-Phenylenediamine-sulphonic acid D 4-Ar1nobenzoyl-p-phenylenediamine sulphonic Do. M aci m-Ihenylene diaznine Do. p-Phenylene diamine Do, 27 d0- Benvidinn D J 1. 28 p-Tolucne-sulphonic acid ester of l-aminq-E-hydroxynaph- 2:7-naphthylene diami'ne slightly yeltha1ene-3:6-disiilphonic acid l'-amino-3.1nethyl-6- lowish red.

methoxybenzene. 29 Benzene-sulphom'c acid esterpf Lamino-S-hydroxynapb. 1:5-di-p-animo;benzoy1-naphthylene-diainine- Do. thalene-3z6-disulphonic acid l-amino-3-methyl-6 3:7-disulphonic acid.

methoxybenzene. r v 1 30 'Bcnzene-siilp'honic a'cidester of 1-aminm8-hydroxgnaph- Benzidine-a-sulphonic acid red.

' thalene-3z6-disulphonic' acid l-amiuo-3 =met yl-6- i 7 g ethoxyben zc ne, w, I '31 do;:" m-Phenylene diamine V ear-ed e -What we claim is: Y wherein-"Y represe z mts' a radical of an aromatic 1. An azo dyestuff' of the formula s I 'di'aminewhose amino groups are in another than (JR o H0 N=NQNH-O O--NHY-NHC o-N-H v H: v

HO;S- x

whereinone X and the correspondirig X1 reprethe o-positionrelativeto each other and which sents H and the other X and the corresponding are free fromazo-chromophores. other-X1 represents SO3H, Y represents a radical '3. An azo dyestuff 'of the formula OCH: I I 01130 HO' N=NQNH-C ONHONH- -CO-NH N=N OH Ht 5503B I H:

i H03 SOgH H035 03K of anaromatic diamine whose amino groups are 4. An.-azo.dyestu1f of the formula 1 (l)CHa I CHaO Ho I!Q'=NNH-C0HN NH-OO-NH N=N OH Ha, Ha

Hots SOaH I 1103s S0311 in=another than the o-position relative to each An azo dyestufi of. the formula OOH: 01130 HO firm-GrapeO-HN-QGmGH-QNH-OO-NEPQMN )11 I (5H3 s03 V I so e 7 H3 1103s SO3H v H i H038 SOaH other and which are free from azo-chromophores 6. An azo dyestuff of the formula OCH: enao 11o N=NQNH-C O-EN-QNEF-C O-NH- N= OH H: i I H3,

HO3S sole e HO3S- s03 and'R represents a lower alkyl group. '7. An azo dyestufi of the formula )0113 01130 HO NzN-QNH-C 0-111? NHCONHQN=N OH om Hs HOaS 'SOaH H038 50311 H038 SOaH ONH 2; An azo dyestufi of the formula (1)0113 QHQO m N=NQNHCO-NH-YNH-CONHQN=N OH BOSS S0811 HOaS- S0311 ERNST KELLER.

FRITZ PROBST. REFERENCES CITED The following references are of record in the Number Name Date file of this patent: 2,846,546 Montmollin et a1. Feb. 23, 1932 UNITED STATES PATENTS I 2,363,844 Keller et a1 Feb. 6, 1945 2,399,066 Schmid et al. Apr. 23, 1946 Number Name Date 11,006,929 Freimann Oct. 24, 1911' 

5. AN AZO DYESTUFF OF THE FORMULA 